EP0878708B1 - Elektrochemischer Biosensor mit einem Deckel - Google Patents

Elektrochemischer Biosensor mit einem Deckel Download PDF

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Publication number
EP0878708B1
EP0878708B1 EP98107765A EP98107765A EP0878708B1 EP 0878708 B1 EP0878708 B1 EP 0878708B1 EP 98107765 A EP98107765 A EP 98107765A EP 98107765 A EP98107765 A EP 98107765A EP 0878708 B1 EP0878708 B1 EP 0878708B1
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EP
European Patent Office
Prior art keywords
sensor
lid
base
layer
electrode layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98107765A
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English (en)
French (fr)
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EP0878708A1 (de
Inventor
Steven C. Charlton
Larry D. Johnson
Matthew K. Musho
Dennis Slomski
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Bayer AG
Bayer Corp
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Bayer AG
Bayer Corp
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Publication date
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Publication of EP0878708A1 publication Critical patent/EP0878708A1/de
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/001—Enzyme electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
    • G01N27/3272—Test elements therefor, i.e. disposable laminated substrates with electrodes, reagent and channels
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S435/00—Chemistry: molecular biology and microbiology
    • Y10S435/817—Enzyme or microbe electrode
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1036—Bending of one piece blank and joining edges to form article
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1039—Surface deformation only of sandwich or lamina [e.g., embossed panels]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1039—Surface deformation only of sandwich or lamina [e.g., embossed panels]
    • Y10T156/1041—Subsequent to lamination

Definitions

  • the present invention relates to an electrochemical biosensor that can be used for the quantitation of a specific component (analyte) in a liquid sample and to a method of manufacturing such a biosensor.
  • Electrochemical biosensors of the type under consideration are disclosed in U.S. patents 5,120,420 and 5,264,103.
  • the devices disclosed in these patents have an insulating base upon which carbon electrodes are printed which electrodes are covered with a reagent layer which comprises a hydrophilic polymer in combination with an oxidoreductase specific for the analyte.
  • a spacer element placed on the base, which element is cut out to provide a generally U shaped piece and a cover piece, so that when the base, spacer element and cover piece are laminated together, there is created a capillary space containing the electrodes and the reagent layer.
  • an electron acceptor on the reagent layer or in another layer within the capillary space.
  • a hydrophilic polymer e.g. carboxymethyl cellulose, is used to facilitate the drawing of the aqueous test fluid into the capillary space.
  • the present invention is concerned with an electrochemical sensor which is comprised of two parts; a lower part (base) which carries the electrode structure and reactants which are deposited as necessary and an upper part (lid) which is embossed to form three sides of a capillary space with the base forming the fourth side upon mating of the lid and base.
  • the base and lid are laminated together, such as, by means of sonic welding.
  • the sensor is used by dipping the open end of the capillary into a small drop of test fluid, such as blood, which is drawn into the capillary tube so that it covers the enzyme and electron acceptor on the electrode's surface.
  • the electrode carries an oxidoreductase and an electron acceptor distributed in a hydratable polymeric matrix on its surface.
  • the polymer matrix Due to the hydratable nature of the polymer matrix, it disperses in the aqueous test fluid thereby allowing the oxidoreductase, which is glucose oxidase when the sensor is designed to determine the concentration of glucose in blood, to oxidize the analyte and the electron acceptor to shuttle the excess electrons to the working electrode thereby creating a measurable current which is proportionate to the concentration of analyte in the test fluid.
  • the oxidoreductase which is glucose oxidase when the sensor is designed to determine the concentration of glucose in blood
  • the two piece sensor construction of the present invention does not require an enzymatic layer.
  • sensors that detect directly at the electrode surface. Examples of such sensors would be those for detecting hematocrit or a sensor for detecting lead in blood.
  • Another class of sensors is those which have a binding or coupling agent over or on the electrode surface which initiates a chemical reaction.
  • a sensor with a binding agent capable of releasing a detectable moiety such as protons when the analyte attaches itself to the agent and measuring the pH change can be prepared according to the present invention.
  • the binding system can be an antigen-antibody pair wherein the antibody could prevent or enhance a reaction at the electrode surface.
  • the manufacture of the prior art sensors as described above involves the use of an extra part, the spacer layer, and a number of processing steps which are not required with the two part sensor (base and lid) with which the present invention is involved.
  • the present sensor is prepared by a straight forward procedure which involves the steps defined in claim 11.
  • the present invention is an electrochemical sensor for the detection of an analyte in a fluid test sample which comprises:
  • the electrode is in operative connection with an enzyme which reacts with the analyte to produce mobile electrons.
  • the construction of the sensor with which the present invention is concerned is illustrated by Fig. 1.
  • the sensor 34 is comprised of insulating base 36 upon which is printed in sequence (typically by screen printing techniques), an electrical conductor pattern 38, an electrode pattern (39 and 40), an insulating (dielectric) pattern 42 and finally a reagent layer 44.
  • the function of the reagent layer is to convert glucose, or another analyte, stoichiometrically into a chemical species which is electrochemically measurable, in terms of current it produces, by the components in the electrode pattern.
  • the two parts 39 and 40 of the electrode print provide the working and reference electrodes necessary for the electrochemical determination.
  • the electrode ink which is about 14 ⁇ (0.00055'') thick, typically contains electrochemically active carbon.
  • Components of the conductor ink are a mixture of carbon and silver, chosen to provide a low chemical resistance path between the electrodes and the meter with which they are in operative connection via contact with the conductor pattern at the fish-tail end of the sensor 45.
  • the typical thickness of the entire structure is 6 ⁇ (0.00025'').
  • the function of the dielectric pattern is to insulate the electrodes from the test sample except in a defined area near the center of the electrode pattern 41 to enhance the reproducibility of the sensor reading. A defined area is important in this type of electrochemical determination because the measured current is dependent both on the concentration of the analyte and the area of the electrode which is exposed to the analyte containing test sample.
  • a typical dielectric layer comprises a UV cured acrylate modified polyurethane about 10 ⁇ (0.0004") thick.
  • the lid 46 which provides a concave space 48, typically formed by embossing a flat sheet of the deformable material, is punctured to provide air vent 50, and joined to the base 36 in a sealing operation.
  • the lid and base are sealed together by sonic welding in which the base and lid are first aligned and then pressed together between a vibratory heat sealing member or horn and a stationary jaw.
  • the horn is shaped such that contact is made only with the flat, non-embossed regions of the lid.
  • Ultrasonic energy from a crystal or other transducer is used to excite vibrations in the metal horn. This mechanical energy is dissipated as heat in the plastic joint allowing the bonding of thermoplastic materials.
  • the procedure is more fully described in U.S. Patents 3,505,136; 3,573,139; 3,562,041 and 4,313,774.
  • Suitable materials for the insulating base include polycarbonate, polyethylene terephthalate and dimensionally stable vinyl and acrylic polymers as well as polymer blends such as polycarbonate/polyethylene terephthalate and metal foil structures such as a nylon/aluminum/polyvinyl chloride laminate.
  • the lid is typically fabricated from a deformable polymeric sheet material such as polycarbonate or an embossable grade of polyethylene terephthalate, glycol modified polyethylene terephthalate or a metal foil composition such as an aluminum foil structure.
  • the dielectric layer can be fabricated from an acrylate modified polyurethane which is curable by UV light or moisture or a vinyl polymer which is heat curable.
  • the present invention facilitates the use of an embossed lid (46, Fig. 1) as opposed to the use of a spacer as in the prior art sensor elements in which, instead of embossing, the two sides of the capillary space are formed from a spacer element.
  • the use of the embossed lid enables one to avoid the use of an extra part, i.e. the spacer, and a number of processing steps.
  • the steps involved in assembling the spacer containing sensor are:
  • the present invention permits one to manufacture a sensor by:
  • the sensors of the present invention can be manufactured by mating an array of lids, i.e. a flat sheet of lidstock material having a plurality of concave indentations embossed therein, with a corresponding array of bases and then punching individual sensors from the array with a die after the lidstock and sheet of base material have been mated and heat sealed.
  • an array of lids i.e. a flat sheet of lidstock material having a plurality of concave indentations embossed therein
  • a large number of sensor lids are fabricated from a rolled sheet of polycarbonate which has been unrolled to provide a flat surface.
  • This sheet is referred to as the lid stock since it will be the source of a multiplicity of lids.
  • a bifunctional coating solution comprising an aqueous polyurethane dispersion, is spread on to one side of a polycarbonate sheet using a wire wound rod or a slot die coater and air dried.
  • This material provides a wettable surface on the inside of the lid to enhance the ability of the capillary space to fill with test fluid.
  • the dried coating thickness is 0.0007" to 0.002" (17 ⁇ to 50 ⁇ ) with the wet coating thickness in the range of 0.0014" to 0.005" (35 ⁇ to 125 ⁇ ) for a typical solids content of 40% to 50%.
  • the bifunctional layer has some tack for a short period after drying and when the sheet is rewound a temporary liner or interleave is introduced in contact with the coating. After a period of a few hours, the initial tack is lost allowing the polycarbonate lid stock to be unrolled without damage to the coating.
  • Suitable materials for the liner are polyolefins or polyethylene terephthalate.
  • the next stage of processing involves embossing of the concave areas and the punching of various holes in the polycarbonate sheet for registration and tracking before slit ribbons of lid stock are rolled up.
  • the base stock typically of polycarbonate, is printed with various inks to form the electrodes and then overcoated with a dielectric layer in a predetermined pattern designed to leave a desired surface of the electrode exposed.
  • the bifunctional material must adhere to the dielectric material when the lid is mated directly to the dielectric layer.
  • the continuous ribbon of lid stock is unwound and passed through a special laminator where it is registered and them combined with a strip of the base stock. After sonic welding, the continuous ribbon of laminate is wound onto a reel.
  • the laminate is passed through punching equipment in which individual sensors are punched from the array preparatory to being placed into a foil blister package for storage.
  • individual sensors are punched from the array preparatory to being placed into a foil blister package for storage.
  • they are packaged in a circular disk having ten individual compartments arranged radially.
  • the disk is made from an aluminum foil/plastic laminate which is sealed to isolate the sensor from ambient humidity and from other sensors with a burst foil cover, which disk is mounted within a specially designed instrument.
  • a knife is driven down through the burst foil into an individual elongated compartment at the end closest to the hub of the disk and then moved radially toward the perimeter of the blister. In doing so, the knife engages the rear (fish tail) of the sensor in that compartment.
  • the sensor tip In use, the sensor tip, containing the opening to the capillary space, is touched to a small drop of the fluid test sample which is typically blood produced by a finger prick.
  • the blood is rapidly drawn up into the capillary space where the interaction with the enzyme is initiated and the instrument is signaled to initiate its timing sequence. It is essential that blood be drawn very rapidly into the capillary space, regardless of its spatial orientation in order that the timing sequence be initiated.
  • the dimensions of the capillary space are typically on the order of 0.125 mm to 0.38 mm (0.005" to 0.015”) in height and 2.5 mm to 3.75 mm (0.1" to 0.15”) in width to facilitate the drawing of blood into the capillary space.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Zoology (AREA)
  • Biochemistry (AREA)
  • Biophysics (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Microbiology (AREA)
  • Biotechnology (AREA)
  • Genetics & Genomics (AREA)
  • Hematology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
  • Steroid Compounds (AREA)

Claims (14)

  1. Elektrochemischer Sensor zum Nachweis eines Analyt in einer flüssigen Testprobe, welcher von unten nach oben umfasst:
    a) eine isolierende Basisplatte;
    b) eine Elektrodenschicht auf der genannten Basisplatte;
    c) einen Deckel aus einem deformierbaren Material, der eine konkave Fläche im Zentralteil davon in solch einer Weise ergibt, dass beim Zusammenbau mit der Basisplatte die Deckel- und die Basisplatte einen Kapillarraum bilden, worin die Elektrodenschicht zum Kontakt mit der flüssigen Testprobe verfügbar ist, die in den Kapillarraum durch Kapillarwirkung gezogen wird, worin der Deckel und die Basis durch Ultraschall-Schweißtechniken zusammengebracht sind.
  2. Sensor gemäß Anspruch 1, worin eine Reaktionsschicht vorliegt, die ein Enzym umfasst, das mit dem Analyt reagiert, um bewegliche Elektronen auf der Elektrodenschicht zu erzeugen.
  3. Sensor gemäß Anspruch 2 mit einer Schicht aus dielektrischem Material, das in einem Muster über der Elektrodenschicht so aufgebracht ist, dass nur ein Teil der Elektrodenschicht gemäß Vorgabe durch das Muster der dielektrischen Schicht zum direkten Kontakt mit der Testflüssigkeit verfügbar ist.
  4. Sensor gemäß Anspruch 3, worin der Deckel so konfiguriert ist, dass seine Kanten mit der dielektrischen Schicht zusammenkommen.
  5. Sensor gemäß Anspruch 3, worin die dielektrische Schicht so konfiguriert ist, dass sie einen Teilbereich der Elektrodenschicht zurücklässt, der zum direkten Kontakt mit den Kanten des Deckels frei bleibt.
  6. Sensor gemäß Anspruch 3, worin das Enzym in der Reaktionsschicht mit einem hydrophilen Polymer kombiniert ist.
  7. Sensor gemäß Anspruch 6, worin die Reaktionsschicht auch einen Elektronenakzeptor enthält.
  8. Sensor gemäß Anspruch 7, worin der Elektronenakzeptor ein Ferricyanid ist.
  9. Sensor gemäß Anspruch 6, worin das hydrophile Polymer Poly(ethylenoxid) ist.
  10. Sensor gemäß einem der Ansprüche 1 bis 9, worin die konkave Fläche durch Prägung einer flachen Folie aus dem deformierbaren Material gebildet ist.
  11. Verfahren zur Herstellung eines elektrochemischen Sensor, wobei man eine Basis, die eine Elektrodenstruktur auf ihrer Oberfläche trägt, mit einem Deckel aus einem deformierbaren Material zusammenbringt, welcher einen konkaven Raum ergibt, um 3 Seiten eines Kapillarraums zu bilden, wobei Deckel und Basis den elektrochemischen Sensor ergeben, der einen Kapillarraum, der offen zur Atmosphäre ist, mit einer Elektrodenstruktur auf der Oberfläche der Basis umfasst und hin zum Kapillarraum frei bleibt, worin der Deckel und die Basis mit einander durch Ultraschallverschweißung verklebt sind.
  12. Verfahren gemäß Anspruch 13, worin die Elektrodenstruktur eine Oxidoreduktase und einen Elektronenakzeptor trägt, die in einer hydratisierbaren Polymermatrix auf der Oberfläche davon verteilt sind.
  13. Verfahren gemäß Anspruch 11, worin die hydratisierbare Polymermatrix aus Poly(ethylenoxid) zusammengesetzt ist.
  14. Verfahren gemäß Anspruch 12, worin die Oxidoreduktase Glucose-Oxidase und der Elektronenakzeptor ein Ferricyanid sind.
EP98107765A 1997-05-12 1998-04-29 Elektrochemischer Biosensor mit einem Deckel Expired - Lifetime EP0878708B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US854439 1997-05-12
US08/854,439 US5798031A (en) 1997-05-12 1997-05-12 Electrochemical biosensor

Publications (2)

Publication Number Publication Date
EP0878708A1 EP0878708A1 (de) 1998-11-18
EP0878708B1 true EP0878708B1 (de) 2005-04-13

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US (1) US5798031A (de)
EP (1) EP0878708B1 (de)
JP (2) JP4201877B2 (de)
AT (1) ATE293251T1 (de)
AU (1) AU724236B2 (de)
CA (1) CA2236132C (de)
DE (1) DE69829707T2 (de)
DK (1) DK0878708T3 (de)
ES (1) ES2241073T3 (de)
NZ (1) NZ329793A (de)
TW (1) TW400433B (de)

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US7674232B2 (en) 2002-04-19 2010-03-09 Pelikan Technologies, Inc. Method and apparatus for penetrating tissue
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US7708701B2 (en) 2002-04-19 2010-05-04 Pelikan Technologies, Inc. Method and apparatus for a multi-use body fluid sampling device
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US7892185B2 (en) 2002-04-19 2011-02-22 Pelikan Technologies, Inc. Method and apparatus for body fluid sampling and analyte sensing
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US7901362B2 (en) 2002-04-19 2011-03-08 Pelikan Technologies, Inc. Method and apparatus for penetrating tissue
US7901365B2 (en) 2002-04-19 2011-03-08 Pelikan Technologies, Inc. Method and apparatus for penetrating tissue
US7909777B2 (en) 2002-04-19 2011-03-22 Pelikan Technologies, Inc Method and apparatus for penetrating tissue
US7909778B2 (en) 2002-04-19 2011-03-22 Pelikan Technologies, Inc. Method and apparatus for penetrating tissue
US7914465B2 (en) 2002-04-19 2011-03-29 Pelikan Technologies, Inc. Method and apparatus for penetrating tissue
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US7988645B2 (en) 2001-06-12 2011-08-02 Pelikan Technologies, Inc. Self optimizing lancing device with adaptation means to temporal variations in cutaneous properties
US8007446B2 (en) 2002-04-19 2011-08-30 Pelikan Technologies, Inc. Method and apparatus for penetrating tissue
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US8079960B2 (en) 2002-04-19 2011-12-20 Pelikan Technologies, Inc. Methods and apparatus for lancet actuation
US8197421B2 (en) 2002-04-19 2012-06-12 Pelikan Technologies, Inc. Method and apparatus for penetrating tissue
US8221334B2 (en) 2002-04-19 2012-07-17 Sanofi-Aventis Deutschland Gmbh Method and apparatus for penetrating tissue
US8262614B2 (en) 2003-05-30 2012-09-11 Pelikan Technologies, Inc. Method and apparatus for fluid injection
US8267870B2 (en) 2002-04-19 2012-09-18 Sanofi-Aventis Deutschland Gmbh Method and apparatus for body fluid sampling with hybrid actuation
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US8337421B2 (en) 2001-06-12 2012-12-25 Sanofi-Aventis Deutschland Gmbh Tissue penetration device
US8360992B2 (en) 2002-04-19 2013-01-29 Sanofi-Aventis Deutschland Gmbh Method and apparatus for penetrating tissue
US8404100B2 (en) 2005-09-30 2013-03-26 Bayer Healthcare Llc Gated voltammetry
US8425757B2 (en) 2005-07-20 2013-04-23 Bayer Healthcare Llc Gated amperometry
US8435190B2 (en) 2002-04-19 2013-05-07 Sanofi-Aventis Deutschland Gmbh Method and apparatus for penetrating tissue
US8556829B2 (en) 2002-04-19 2013-10-15 Sanofi-Aventis Deutschland Gmbh Method and apparatus for penetrating tissue
US8574895B2 (en) 2002-12-30 2013-11-05 Sanofi-Aventis Deutschland Gmbh Method and apparatus using optical techniques to measure analyte levels
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CA2236132A1 (en) 1998-11-12
AU6482198A (en) 1998-11-12
JP2008286809A (ja) 2008-11-27
US5798031A (en) 1998-08-25
EP0878708A1 (de) 1998-11-18
TW400433B (en) 2000-08-01
DK0878708T3 (da) 2005-07-11
JP4201877B2 (ja) 2008-12-24
JP4224130B2 (ja) 2009-02-12
DE69829707T2 (de) 2006-03-02
ATE293251T1 (de) 2005-04-15
CA2236132C (en) 2004-07-20
DE69829707D1 (de) 2005-05-19
JPH10318971A (ja) 1998-12-04
NZ329793A (en) 1998-11-25
AU724236B2 (en) 2000-09-14
ES2241073T3 (es) 2005-10-16

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